CN104276564B - A kind of application of carbonization microsphere - Google Patents
A kind of application of carbonization microsphere Download PDFInfo
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- CN104276564B CN104276564B CN201410591425.4A CN201410591425A CN104276564B CN 104276564 B CN104276564 B CN 104276564B CN 201410591425 A CN201410591425 A CN 201410591425A CN 104276564 B CN104276564 B CN 104276564B
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Abstract
The invention provides the application of a kind of carbonization microsphere, this carbonization microsphere, with the polymer microballoon containing vinyl aromatic monomers as raw material, obtains after heated carbonization.Described carbonization microsphere is used as fullerene and the chromatograph packing material of carbon nanotube separation purification mutually as fixing, flow velocity increases substantially, and disengaging time is short, and chromatographic column is forced down, good separating effect, is suitable for the fast separating and purifying of the carbon allotrope nano material such as fullerene and CNT.
Description
Technical field
The present invention relates to chromatographic isolation field, be specifically related to a kind of carbonization microsphere at carbon allotrope
Application in the separation of body nano material.
Background technology
The allotrope of elemental carbon includes that fullerene and CNT, two kinds of materials all contain five limits
Shape and the annular polygonal structure of hexagonal carbocyclic ring composition.Owing to its structure connects perfection, tool
There are many abnormal mechanics, electricity and chemical property.
The material of fullerene (Fullerene) class comprises the C being such as made up of 60 carbon atoms60
-" bucky-ball " (Buckminsterfullerene), has abnormal stability, and has ball
Shape symmetrical structure.Fullerene has molecular structure and physicochemical properties, the C of uniqueness60In for
The compound of empty football shaped, inside its molecular ball, the different element of doping can produce superconductivity
Matter, fullerene has a strongest electron acceptability, excellent nonlinear optical property, therefore
Fullerene the most constantly shows in the broad prospect of application of the subjects such as physics, chemistry, material.
The radial direction of CNT axially up to micron dimension, has typical layer for nanometer scale
Shape hollow structure feature.CNT can be divided into list according to the number of plies of the carbon atom forming tube wall
Wall carbon nano tube and multi-walled carbon nano-tubes, wherein multi-walled carbon nano-tubes is appreciated that as straight by difference
Footpath SWCN suit forms.In actual applications, SWCN, the number of plies are less
Multi-walled carbon nano-tubes have prominent performance to have consequence.
Recently as to nano material in-depth study, the allotrope of above two kinds of elemental carbons
Body material broad prospect of application the most constantly shows, because the purity of material itself is to electricity
The aspect application performances such as, mechanics and optics have significant effect, to separation in its preparation process
The requirement of purification constantly improves.D.Huffman and W.Kraetschmer et al. is in 1990
Annual report can arc process preparation amount is more under an inert atmosphere C60、C70And higher carbon number
Fullerene mixture.Fullerene has molecular structure and physicochemical properties, the fowler of uniqueness
Alkene C60For the compound of the football shaped of hollow, inside its molecular ball, the different element of doping can produce
Raw superconducting property, fullerene has the strongest electron acceptability, excellent optically nonlinearity
Matter, thus relevant fullerene prepare isolated and purified become a very active field.
The fullerene mixture produced from arc process typically uses organic solvent extraction and separation, mainly
Composition C60And C70Ratio about between 75: 25 to 85: 15.From fullerene mixture
Separate and prepare pure C60And C70Or higher fullerene is a job the most difficult, due to that
This molecular structure is closely similar, and physicochemical properties are the most close, and the isolated and purified of product has
Bigger difficulty.
First Nacalai Tesque Inc. company of Japan produces containing pyrenyl and phenyl-pentabromide ethyl
The silica gel chromatographic column filling material of functional group, can separate fullerene product (Japan Patent JP
2003-360670), present laboratory the most all uses the richness of Nacalai Tesque Inc. company
Strangle alkene and divide analysis of variance chromatographic column.But, this silica matrix fixes the preparation process of phase very
Complicated；Additionally the chemical characteristic of silica gel itself determines the functional group stability of surface bond relatively
Difference, therefore the life-span is shorter；The more important thing is, this silica gel chromatographic column filling material is only capable of meeting laboratory
Need, and fullerene large-scale production cannot use the chromatograph that fixing phase preparation process is extremely complex
Post, the most this silica gel chromatographic column filling material is not suitable with industrialization large-scale production.
In order to be able to fullerene product of accomplishing scale production, it is necessary for exploitation a kind of efficient and suitable
The new chromatographic separating filler of the most extensive preparation.
Chinese invention patent (CN1108271) discloses a kind of efficient for Separation of fullerenes
The manufacture method of Stationary Phase for HPLC, the macroporous polystyrene of employing-divinyl phenyl ball be with
Styrene be raw material, divinylbenzene be cross-linking agent, then will be with C60、C70Intermolecular force
Stronger 2-(3,4-xylyl) ethyl is received on base ball as separation function group.This fixing phase can
With with 0-dimethylbenzene for flowing be separated C60、C70And higher fullerene.Chinese invention patent
(CN1114656) a kind of Stationary Phase of HPLC for Separation of fullerenes is disclosed
The modified macroporous polystyrene-divinylbenzene of 2-(3,5-xylyl) ethyl fixes the preparation side of phase
Method, uses two step Friedel-Crafts reactions, macroporous polystyrene-divinyl phenyl ball and 1,2-
Dichloroethanes reacts, by-CH2-CH2C1 group is connected on base ball, then reacts with m-dimethylbenzene,
Make the fixing phase with 2-(3,5-xylyl) ethyl group.This is fixed and can use 0-diformazan mutually
Benzene is flowing phase, high efficiency separation C60And C70.But, micro-sphere crosslinked degree prepared by the method is relatively
Low, hardness is less, the most swelling in toluene and o-Dimethylbenzene, thus post pressure is higher, thus
Limit its flow velocity in chromatographic applications, this fixing stream allowing flowing phase mutually of 8-15 μm
Speed is only 0.15-0.25mL/min, prepares the sample first separation time at more than 200min.
Its large-scale application of existing drawbacks limit.
" 2，4，6-trinitrophenol modification zirconia-magnesia composites fixes Separation of Fullerenes to document
Chromatographic performance research " and ([J]. chromatograph, 2005,23 (4): 384-388.) in disclose a kind of with 2,4,
6-trinitrophenol modification zirconia-magnesia composites is as the method for fixing Separation of Fullerenes.Grind
Also attempted use bromination before the person of studying carefully and pyrenyl functionalization prepared fullerene preparative separation filler,
The preparation method proposed such as Chinese invention patent CN102659966, CN102863640, available
In isolated and purified fullerene.But these prior aries are longer for separation or the needs of fullerene
Time, separation efficiency is low；Or separating filler all uses chemosynthesis, and not only step is complicated,
And chemical raw material used and solvent typically have bigger toxicity, easily cause the person and environment
Injury, has the highest burden to operating environment and human users.
Summary of the invention
It is an object of the invention to the deficiency overcoming prior art to exist, it is provided that a kind of separation efficiency
The extensive isolated and purified fullerene of industrialization high, effective, applicable and the method for CNT.
For reaching above-mentioned purpose, the technical scheme is that the application of a kind of carbonization microsphere,
Described carbonization microsphere is as the fixing chromatographic separation and purification being applied to fullerene and CNT mutually
In.
Wherein, described fullerene and CNT isolated and purified in, flowing be mutually aromatic hydrocarbon,
At least one in non-aromatic hydrocarbon.
Wherein, the described aromatic hydrocarbon as flowing phase is at least one in benzene, toluene.
Wherein, the described non-aromatic hydrocarbon as flowing phase is at least in chloroform, dichloromethane
Kind.
Wherein, described fullerene and CNT isolated and purified in, flowing can also is that two mutually
At least one in nitric sulfid, quinoline, oxolane, thiophene, Tetramethylene sulfide.
Wherein, described carbonization microsphere is former with the polymer microballoon containing vinyl aromatic monomers
Material, obtains after heated carbonization.
Wherein, carbonization temperature of heating described in is 400～500 DEG C.
Wherein, carbonization time of heating described in is 4～10 hours.
Wherein, the diameter range of the described polymer microballoon containing vinyl aromatic monomers is 5～40
μm。
Wherein, the pore diameter range of the described polymer microballoon containing vinyl aromatic monomers is
2～100nm.
Wherein, described at least one mono vinyl aromatics list is comprised containing vinyl aromatic monomers
Body.
Wherein, described at least one many vinyl aromatics list is comprised containing vinyl aromatic monomers
Body.
Wherein, the carbonization microsphere obtained is successively by acetone, ethanol, water, washing with alcohol, vacuum
Obtain the carbonization microsphere being dried after drying.
Suitably containing vinyl aromatic monomers including, but not limited to becoming known for polymerization process
Vinyl aromatic monomers, such as disclosed in United States Patent (USP) (US Pat.4572819)
Vinyl aromatic monomers, typical vinyl aromatic monomers includes: styrene, methylbenzene
Ethylene, all isomers of vinyltoluene and to vinyltoluene, ethyl styrene
All isomers, propylstyrene, vinyl naphthalene, vinyl anthracene and its mixture.Ethylene
Base aromatic monomer can also be copolymerizable with other monomer combine.The example bag of such monomer
Include but be not limited to alkene nitrile and acrylic ester monomer, as acrylonitrile, methacrylonitrile, third
Olefin(e) acid ester, methacrylate and mixture thereof.
The monomer of above polyreaction also can comprise at least one many vinyl aromatic monomers,
Described many vinyl aromatic monomers include by divinylbenzene, one and to a divinyl
The mixture of benzene, trivinylbenzene, divinyl toluene, divinylxylene, divinyl
Base naphthalene, and derivant.These compounds can be individually or with two kinds or above mixture
Use.Particularly preferred many vinyl aromatic monomers mixture is by asking one and to a divinyl
Benzene forms.
Monodisperse polymer micro-sphere can be prepared via different methods, and polymer of the present invention is micro-
Ball is to be prepared by polyreaction；Polyreaction includes emulsion polymerization, emulsifier-free emulsion polymerization, micro-
Emulsion polymerization, mini-emulsion polymerization, dispersin polymerization, suspension polymerisation and seeding polymerization, be suitable for this
Bright polyreaction such as dispersin polymerization, suspension polymerisation and seeding polymerization, be particularly suitable for the present invention
Polyreaction such as suspension polymerisation and seeding polymerization, seeding polymerization has multiple different method real
Execute, such as Chinese invention patent (CN101186661B), entitled " a kind of polymer beads
Preparation method " be used for preparing single point and disclose and a kind of use seed to carry out being polymerized and swelling simultaneously
Manufacture method, Chinese invention Publication No. CN1362973A, entitled " be used for preparing list
The method of dispersed polymeres particle " patent of invention in, propose make monomer and include that single dispersing can
The aqueous dispersion contact of swelling seed polymer Zhi polymers, causes poly-in the presence of stabilizer
Close and form microsphere.
The polymer microballoon of the present invention can be formed with pass, and general pore type generally contains only poly-
The intermolecular hole of compound itself, its pore diameter is less than about 1nm, and macroporous type granule then contains
Having the additional hole unrelated with intermolecular hole, its pore diameter at least about 2nm, big
In polymer beads, its pore diameter can reach hundreds of nanometer or near micrometer range, gathers little
In polymer beads, this diameter is more relatively small, when the monomer joined in seed grain or monomer mix
When not having perforating agent in thing, the polymer beads of generation is by simply pore type, but works as containing pore-forming
During agent, granule will be just macroporous type.The polyreaction being formed with cell polymeric is published in the U.S.
In patent (US Pat.4382124), perforating agent is the solvent of the monomer mixture of polymerization,
But insoluble polymer so that polymer once generate just from monomer mutually separate, when
The polymer concentration generated in microsphere increases, and perforating agent is repelled extrusion by polymer and stays mutually
Hole even is in polymer microballoon.The perforating agent being suitable for the present invention has C4～C10Alkanol
Including butanol, the amylalcohol of straight or branched, hexanol enanthol, capryl alcohol, nonyl alcohol, decanol, such as
4 monomethyl amyl groups 1 alcohol (methyl isobutyl carbinol)；Seven or the alkyl of more carbon atom
Ester such as Exceed 600, acetic acid 1 Octyl Nitrite, methyl oleate, dibutyl sebacate,
Dibutyl adipate and dibutyl carbonate；Aliphatic ketone such as methyl iso-butyl ketone (MIBK), diisobutyl
Ketone；And aromatic hydrocarbon such as toluene, para-position, ortho position dimethylbenzene, or mentioned above suitable
Mixture.
Chromatographic isolation analytical technology, along with continuously improving and developing, has become application pole the most
The important means analyzed for Chemical Decomposition widely, chromatography is to exist based on mixture to be separated
Relative motion thing biphase between distribution time, chemically or physically the difference of character and make mixture phase
The class separated mutually separates or the method for analysis.It is developed at the beginning of last century, develops rapidly existing so far
Numerous applications.It rationale here is that dividing by a fixing phase that flows mutually with one
Carry out the component in separating mixture from effect, chromatographic column is that the microsphere filler filling of small particle forms
For fixing phase, flowing is that solvent contains and is dissolved in mixture therein and flows through fixing phase, sample mutually
In with the fixing component having stronger affinity mutually fixing mutually in the time of staying longer, with fixing
The more weak component of phase affinity flows out chromatographic column the most faster, thus reaches separation and be dissolved in flowing
The effect of different molecular in phase solvent.Therefore fix the composition of phase and the selection of flowing phase is chromatograph
Separate the core technology analyzed.
The present invention discloses the application of a kind of carbonization microsphere as mentioned above, and described carbonization microsphere is as solid
In the fixed chromatographic separation and purification being applied to fullerene and CNT mutually.Have selected fixing phase
In the case of, kind and the proportioning of flowing phase will play very important work to the separating effect of component
With, and flowing is that the kind of solvent is a lot of mutually, selects to be suitable for separate each in liquid chromatography
The flowing of component is a critically important job mutually.Flowing mutually can not with fixing occur mutually irreversible
Chemical reaction, do not change the character of fixing phase, but the component in sample should be had suitable molten
Xie Du, when dissolubility is the least, sample can produce precipitation in flowing mutually, and to each component
Dissolubility should have difference；The viscosity of flowing phase should be less, can reduce the resistance of chromatographic column；Stream
The recovery of dynamic relative sample does not interferes with, and easily cleans after using；Flow necessary with detector
Match.
Based on the above, the flowing that the present invention uses must be chosen from solubilized material to be separated mutually
Solvent, such as, separate the flowing of fullerene and be selected from the organic or inorganic solvent of fullerene mutually and include
But being not limited to aromatic series and non-aromatic solvent, non-aromatic solvent includes ring-type, non-annularity and
It mixes shape solvent, and the most above-mentioned solvent molecule can contain halogen, and one or more than one is not
Saturated bond, relevant fullerene C60Various solvents see Fullerene Science and
Technology, 5 (2), 291-310 (1997).Preferably solvent includes non-aromatic hydrocarbon
(nonaromatic hydrocarbon), aromatic hydrocarbon (aromatic hydrocarbon) and its spread out
Biological solutions.Non-aromatic hydrocarbon mainly with halogenated hydrocarbons (haloalkane) as representative, the most preferably
Solvent includes chloroform (chloroform) and dichloromethane (dichloromethane)；Preferably
It is aromatic hydrocarbon, mainly with benzene, toluene as representative；Other preferable solvent also has Carbon bisulfide, quinoline
Quinoline, oxolane, thiophene and Tetramethylene sulfide etc.；Above-mentioned solvent is mutually mixed, it is also possible to as
The flowing phase of fullerene chromatographic isolation.The application of carbonization microsphere disclosed by the invention, is with above-mentioned
Carbonization microsphere is applied to fullerene and CNT mutually as the fixing suitable flowing that matches
Chromatographic separation and purification, compared with prior art achieves following beneficial effect:
1, the carbonization microsphere of the present invention is used as Stationary Phase for HPLC as a kind of brand-new material,
Relative to separating the fixing phase of fullerene in prior art, flow velocity increases substantially, and either divides
From efficiency, or sample disengaging time, all show more satisfactory separating effect, and energy
Reduce use and the maintenance cost of required instrument, be suitable for fullerene and CNT quick,
Efficiently, the most isolated and purified.
2, the carbonization microsphere of the present invention is the most swelling in the solvent of fullerene is as chromatogram flow phase,
Therefore chromatographic column pressure is little, about the 30% of the most close specification silica filler post pressure, thus can make
With high flow velocity, improve efficiency.
3, the carbonization microsphere of the present invention is micro-with the monodisperse polymer containing vinyl aromatic monomers
Ball is base ball, uniform particle diameter, and pore-size distribution is concentrated, and makes the particle diameter of the carbonization microsphere prepared
More uniform, pore-size distribution is concentrated, and adds carbonization microsphere surface and only has C-C key, is particularly suitable for
In separating fullerene and the allotrope nano material of this kind of elemental carbon of CNT.
Accompanying drawing explanation
Fig. 1 is the charcoal ball SEM figure of the raw material ball used by embodiment 1 and preparation.Fig. 1 a is former
Pellet, Fig. 1 b is the carbonization microsphere prepared.
Fig. 2 is charcoal ball and the monodisperse polymer containing vinyl aromatic monomers of embodiment 1 preparation
The infrared spectrum comparison diagram of thing microsphere.
Fig. 3 is that the carbonization microsphere of embodiment 1 preparation is as fixing for the color separating fullerene
Spectrogram.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is further described, but this
Invention is not limited to these embodiments.
Embodiment 1,
Use Suzhou Nano-micro Technology Co., Ltd.30-300 series contains vinyl aromatic
The monodisperse polymer micro-sphere of race's monomer is base ball.10.00g is first weighed in dry pallet
This polymer microballoon (particle diameter is 30 μm, and aperture is about 30nm), shakeout and join 150
In mm × 150mm × 30mm pallet, level puts into Muffle furnace afterwards, temperature programming to 420
DEG C to ensure reacting balance, carbonization reaction 4-6 hour.After completion of the reaction, first Muffle furnace is dropped
To room temperature.This carbonization microsphere is used acetone, ethanol, water, washing with alcohol successively, and vacuum is done
The carbonization microsphere (being denoted as Nano-C) being dried, about 3.23g is obtained after dry.
Monodisperse polymer micro-sphere SEM figure as the vinyl aromatic monomers of base ball is shown in attached
Fig. 1 a.The carbonization microsphere SEM figure of preparation is shown in accompanying drawing 1b.After visible carbonization processes, microsphere
Amassing and reduce, microspherulite diameter is more uniform, spherical the most relatively regular
Accompanying drawing 2 is carbonization microsphere (Nano-C) and the vinyl aromatic polymerization of embodiment 1 preparation
Thing microsphere base ball (Infrared spectrogram 30-300).It is visible, before carbonization processes
Aromatic hydrocarbon c h bond (2960～2850cm in 30-300-1) linkage content carbonization process after significantly
Reducing, aromatic hydrocarbon is at 1600cm-1, 1580cm-1, 1500cm-1And 1450cm-1Place absorbs
Peak is also close to disappearance, explanationIn 30-300, a considerable amount of benzene ring structures are by carbonization.
Carbonization microsphere surface only has C-C key substantially, does not has the functional group that other are elementary composition, especially
The allotrope nano material being suitable for separating the elemental carbons such as fullerene is this kind of all by carbon group
The material become, isolated and purified effect is the best.
Take product microsphere 2g prepared by the present embodiment, load by slurry method under 1000psi pressure
In the rustless steel chromatographic column of 250 × 4.6mm.Then this post is contained in Yi Lite high-efficient liquid phase color
On spectrometer, the toluene using 100% is as flowing phase, and flow velocity is 1mL/min, and detection wavelength is
600nm, injects the fullerene crude product that 20 μ L concentration are 4.4mg/ml.Separating resulting figure is shown in
Accompanying drawing 3, C60And C70Retention time be respectively 3min and 4min, post pressure ＜ 1MPa.
Collect purification C60Component, its purity is up to ＞ 99%.Visible, carbonization microsphere can be by C60With
C70Fast separating and purifying.
The present embodiment selects particle diameter to be 30 μm, and aperture is about the vinyl aromatic list of 30nm
Body monodisperse polymer micro-sphere is base ball so that diameter and the aperture of the carbonization microsphere of preparation also exist
In one approximate range, microsphere diameter is about 10～20 μm, is used as the fixing phase of liquid chromatograph,
Relative to separating the fixing phase of fullerene in prior art, flow velocity can increase substantially, either
Separation efficiency, or sample disengaging time, all show preferable separating effect, be suitable for
Fullerene quickly detects.
Embodiment 2
Reaction unit is same as in Example 1, uses Suzhou Nano-micro Technology Co., Ltd.
The monodisperse polymer micro-sphere of 10～300 series vinyl base aromatic monomers.Reaction controlling and wash ball
Step is with embodiment 1.The carbonization microsphere obtaining after vacuum drying being dried is about 3.38g.
With reference to embodiment 1, take product microsphere 2g prepared by the present embodiment, at 1000psi pressure
Lower slurry method loads in the rustless steel chromatographic column of 250 × 4.6mm.Then this post is contained in and depends on
On the special high performance liquid chromatograph of profit, the toluene using 100% is as flowing phase, and flow velocity is 1
ML/min, detection wavelength is 600nm, and injecting 20 μ L concentration is the fowler of 4.4mg/ml
Alkene crude product.C60And C70Retention time be respectively 3.5min and 4.5min, post pressure is about 1.5
MPa.This carbonization microsphere visible is capable of the sharp separation of fullerene material.
Embodiment 3,
Use the Cosmosil Buckprep that Nacalai Tesque Inc. company producesTMFowler
(in post, filler is polydispersity microsphere to alkene dedicated separation post, mean diameter 5 μm, about hole
Footpath) carry out performance comparison with the carbonization microsphere chromatographic column of the present invention.Test condition is with implementing
Example 1.
Test result is, Cosmosil BuckprepTMFullerene dedicated separation post can realize C60
And C70Complete baseline separation, C60And C70Retention time is respectively 8min and 12min,
Corresponding post pressure is about 5MPa.
Table 1. carbonization microsphere separates the comparison of fullerene with general microsphere
Visible, the carbonization microsphere of present invention application has in terms of the sharp separation and post pressure of fullerene
Preferably advantage.
The invention provides a kind of carbonization microsphere at the carbon allotrope such as fullerene and CNT
Application on class nano material material is isolated and purified, this carbonization microsphere is with containing vinyl aromatic list
The polymer microballoon of body is raw material, obtains after carbonization of heating, and it is filled out as the fixing chromatograph that is used as mutually
Material, the flow velocity of flowing phase can increase substantially, and disengaging time is short, good separating effect, is suitable for
Fullerene sharp separation.
Above-described is only the preferred embodiment of the present invention, it is noted that for this area
Those of ordinary skill for, without departing from the concept of the premise of the invention, it is also possible to do
Going out some deformation and improvement, these broadly fall into protection scope of the present invention.
Claims (11)
1. the application of a carbonization microsphere, it is characterised in that described carbonization microsphere is as fixing corresponding
In the chromatographic separation and purification of fullerene and CNT；
Described carbonization microsphere with the polymer microballoon containing vinyl aromatic monomers as raw material, heated charcoal
Obtain after change；
Described fullerene is to be separated selected from solubilized mutually with the flowing of the chromatographic separation and purification of CNT
The solvent of thing.
2. the application of carbonization microsphere as claimed in claim 1, it is characterised in that described fullerene
With CNT isolated and purified in, flowing be at least one in aromatic hydrocarbon, non-aromatic hydrocarbon mutually.
3. the application of carbonization microsphere as claimed in claim 2, it is characterised in that described as stream
The aromatic hydrocarbon of dynamic phase is at least one in benzene, toluene.
4. the application of carbonization microsphere as claimed in claim 2, it is characterised in that described as stream
The non-aromatic hydrocarbon of dynamic phase is at least one in chloroform, dichloromethane.
5. the application of carbonization microsphere as claimed in claim 1, it is characterised in that described fullerene
With CNT isolated and purified in, flowing can also is that mutually Carbon bisulfide, quinoline, oxolane,
At least one in thiophene, Tetramethylene sulfide.
6. the application of carbonization microsphere as claimed in claim 1, it is characterised in that described in heat charcoal
The temperature changed is 400～500 DEG C, and carbonization time is 4～10 hours.
7. the application of carbonization microsphere as claimed in claim 1, it is characterised in that described containing ethylene
The polymer microballoon of base aromatic monomer is the porous mono-dispersion microsphere that uniform particle diameter, surface are porose.
8. the application of carbonization microsphere as claimed in claim 1, it is characterised in that described containing ethylene
A diameter of 5～40 μm of the polymer microballoon of base aromatic monomer.
9. the application of carbonization microsphere as claimed in claim 7, it is characterised in that described containing ethylene
The pore diameter range of the polymer microballoon of base aromatic monomer is 2～100nm.
10. the application of carbonization microsphere as claimed in claim 1, it is characterised in that described containing ethylene
Base aromatic monomer comprises at least one mono-vinyl aromatic monomer.
The application of 11. carbonization microspheres as claimed in claim 1, it is characterised in that described containing ethylene
Base aromatic monomer comprises at least one many vinyl aromatic monomers.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1108271A (en) * | 1994-12-23 | 1995-09-13 | 清华大学 | Method for mfg. fixed phase of high efficiency liquid phase chromatogram for separating fulvene |
| CN1132213A (en) * | 1995-03-31 | 1996-10-02 | 中国科学院化学研究所 | Prepn. of Liquid-phase chromatography-use graininess single dispersion, large hole cross-linked polystyrene microballs |
| CN101830457A (en) * | 2010-05-20 | 2010-09-15 | 湖南大学 | Method for preparing carbon microspheres and application of heteropolyacid in carbon microsphere preparation and graphitization |
| CN102659966A (en) * | 2012-04-13 | 2012-09-12 | 苏州纳微生物科技有限公司 | Polymer microsphere, preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61159487A (en) * | 1984-12-29 | 1986-07-19 | Kawasaki Steel Corp | Production of optically anisotropic globule |
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2014
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1108271A (en) * | 1994-12-23 | 1995-09-13 | 清华大学 | Method for mfg. fixed phase of high efficiency liquid phase chromatogram for separating fulvene |
| CN1132213A (en) * | 1995-03-31 | 1996-10-02 | 中国科学院化学研究所 | Prepn. of Liquid-phase chromatography-use graininess single dispersion, large hole cross-linked polystyrene microballs |
| CN101830457A (en) * | 2010-05-20 | 2010-09-15 | 湖南大学 | Method for preparing carbon microspheres and application of heteropolyacid in carbon microsphere preparation and graphitization |
| CN102659966A (en) * | 2012-04-13 | 2012-09-12 | 苏州纳微生物科技有限公司 | Polymer microsphere, preparation method and application thereof |
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